EP1945567B1 - Verbessertes verfahren zur gewinnung von kaliumsulfat (sop, sulphate of potash) aus sulfatreicher muttersole - Google Patents

Verbessertes verfahren zur gewinnung von kaliumsulfat (sop, sulphate of potash) aus sulfatreicher muttersole Download PDF

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EP1945567B1
EP1945567B1 EP05850953A EP05850953A EP1945567B1 EP 1945567 B1 EP1945567 B1 EP 1945567B1 EP 05850953 A EP05850953 A EP 05850953A EP 05850953 A EP05850953 A EP 05850953A EP 1945567 B1 EP1945567 B1 EP 1945567B1
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Prior art keywords
dpa
kcl
schoenite
sop
solution
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EP1945567A1 (de
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Parimal Paul
Pushpito Kumar Ghosh
Kaushik Jethalal Langalia
Palani Sivagnana Subramanian
Suresh Eringathodi
Subrata Patra
Pragati Agnihotri
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Council of Scientific and Industrial Research CSIR
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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C01D3/06—Preparation by working up brines; seawater or spent lyes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to a novel integrated process for the production of sulphate of potash (SOP) from sulphate-rich bittern. More specifically the process relates to recovery of KCl in concentrated solution form from liquid effluent generated during transformation of kainite into schoenite using dipicrylamine as recyclable extractant and use of the KCl solution as per the known prior art for preparation of sulphate of potash from schoenite.
  • SOP sulphate of potash
  • SOP is a dual fertilizer containing 50% K 2 O and 18% Sulphur. It has the lowest salt index and is virtually free of chloride, which makes it a superior fertilizer to muriate of potash (MOP).
  • MOP is easy to produce especially when brine/bittern is low in sulphate content such as in the Dead Sea and this accounts for its lower price compared to SOP.
  • countries such as India, which do not have low sulphate bittern, but which have adequate bittern of sea and sub-soil origin, would be greatly benefited if SOP can be produced economically from such bittern sources.
  • potassium sulphate has numerous industrial applications as well.
  • Solid mixture of potassium chloride and sodium chloride is purified using known techniques to produce pure potassium chloride.
  • the drawbacks of this process are that it fails to make use of the sulphate content in bittern and, instead, offers an elaborate process for manufacture of MOP, which, in any case, is inferior to SOP as fertilizer.
  • the main drawbacks of the process are: (i) the need for floatation which involves use of organic chemicals whose disposal is problematic, (ii) need for external heat for the purpose of recovery of SOP from schoenite through fractional crystallization at elevated temperature, (iii) need for recycling of as much as 30% of K to evaporation ponds where again it gets contaminated with other components of the brine.
  • the sulfate mother liquor is recycled to the kainite - schoenite conversion stage.
  • the main drawbacks of the process are that there is no mention of the fate of the mother liquor obtained upon conversion of kainite into schoenite which would inevitably entail considerable loss of K, and the need for external source of heat to effect the fractional crystallization of SOP.
  • the method comprises concentrating the bittern, separating NaCl, concentrating to obtain crude K-Mg salt containing 10-45% NaCl, crushing, mixing with saturated bittern to obtain a solution with concentration of 20-40%, removing NaCl by back-floatation, concentrating, dewatering to obtain refined K-Mg salt containing less than 5% NaCl, mixing the K-Mg salt and water at specified ratio, allowing the mixture to react at 10-60°F for 0.5-3hr, separating to obtain schoenite, mixing with KCl and water at specified ratio, allowing the mixture to react at 10-70°F for 0.25-3hr and separating to obtain K 2 SO 4 .
  • the drawbacks of the process are (i) need for elaborate method of purification of mixed salt that includes removing NaCl by the less desirable method of back floatation that involves use of organic chemicals, (ii) lack of any mention of the manner in which the various effluent streams are dealt with, and (iii) dependence on outsourced KCl since no mention is made of any process for KCl production as part of the process.
  • bittern is evaporated at a temperature between 100-120°C, thereby forming a solid mixture of sodium chloride and kieserite (MgSO 4 .H 2 O), separating this mixture under hot conditions in a heated centrifuge, and cooling the mother liquor in a cooler for separation of carnallite. Carnallite is decomposed and washed with water to produce potassium chloride.
  • the drawback of this process is that it is demanding in terms of energy requirement and sufficiently pure carnallite cannot be obtained.
  • the main drawback of the process is the contamination of kieserite with NaCl which would necessitate further purification to obtain products in saleable form.
  • Another drawback of the process is that it requires energy to remove sulphate from bittern in the form of kieserite whereas it would be preferable to utilize the sulphate for the production of SOP.
  • Cisoka 1084492 assigned to Lu Zheng describes the process of manufacture of SOP from bittern and potassium chloride.
  • bittern is processed by evaporation, cooling, floatation and then it is reacted with potassium chloride to make potassium sulfate and by-products of industrial salt and residual brine.
  • the main drawbacks of this process are that it requires involved separation techniques like floatation to remove NaCl from mixed salt and KCl required for production of SOP from schoenite has to be procure separately.
  • overall yield in terms of potash recovery is 95%, yield with respect to such procured KCl is not mentioned.
  • the schoenite is then treated with KCl and water to obtain SOP and a filtrate that can be recycled in the step involving conversion of kainite mixed salt into schoenite.
  • the drawback of this process is that the production of KCl from SEL through carnallite intermediate is lengthy, involves co-generation of Mg(OH) 2 , and requires evaporation of large amounts of water. Thus while it is useful to generate KCl from waste, an improved process would be highly desirable.
  • German patent DE 726545, 1942 "Extracting potassium from dilute solutions, e. g., sea water", assigned to E. Berner, and J. Kielland, describes the use of highly nitrated, secondary aromatic amines, e. g, hexanitromethyldiphenylamine or pentanitromethyldiphenyl-amine for the extraction of potassium.
  • the drawbacks of this process are that isolation of solid salt from the dilute aqueous solution is energy intensive and no definite advantage was undertaken for direct use of the aqueous solution.
  • the main object of the invention is to provide a novel integrated process for the production of sulphate of potash (SOP) from sulphate-rich bittern generated during production of schoenite from kainite mixed salt.
  • SOP potash
  • Another object of the present invention is to utilize such KCl obtained in the form of concentrated solution directly for the preparation of sulphate of potash (SOP) through the reaction with schoenite.
  • Still another object of the present invention is to dispense with the requirement of water in the reaction between KCl and schoenite to form SOP, such water being already present in the concentrated KCl solution.
  • Yet another object of the present invention is to utilize dipicrylamine (DPA) as recyclable ligand to extract out K + selectively from SEL without recourse to any evaporation.
  • DPA dipicrylamine
  • Yet another object of the present invention is to treat DPA with slight excess of inexpensive lime slurry to convert it completely into water soluble Ca(DPA) 2 which reacts with the K + in SEL to form K(DPA) while releasing Ca 2+ that can react with the SO 4 2- in SEL to precipitate out gypsum (CaSO 4 ) simultaneously.
  • Yet another object of the present invention is to treat the crude mixture of K(DPA) and gypsum with HCl to leach out 90-95% of the K + in the form of a concentrated KCl solution leaving a residue of gypsum, DPA and small quantities of unreacted K(DPA).
  • Yet another object of the present invention is to obtain KCl in concentrated solution form that can be used directly in the SOP forming reaction.
  • Yet another object of the present invention is to obtain KCl solution of required purity (>90%).
  • Yet another object of the present invention is to treat the small quantities of unreacted K(DPA) remaining along with gypsum and DPA with aqueous HNO 3 to decompose the complex completely so as to eliminate DPA losses in gypsum, recover maximum amount of k + , and to purify the gypsum.
  • Yet another object of the present invention is to treat the residue of gypsum and DPA with slight excess of lime slurry to solubilise the DPA completely in the form of Ca(DPA) 2 leaving behind pure gypsum.
  • Yet another object of the present invention is to devise a cyclic process with complete utilization of all aqueous washings and which yields concentrated solutions of KCl and KNO 3 .
  • Yet another object of the present invention is to devise a process that can operate under ambient conditions.
  • Yet another object of the present invention is to have a process for faster recovery of KCl from SEL through the steps of precipitation and decomposition of K(DPA).
  • Yet another object of the present invention is to produce SOP economically on standalone basis with gypsum and small quantity of KNO 3 as by-products.
  • the present invention provides a integrated process for the production of sulphate of potash (SOP) from sulphate-rich bittern from kainite type mixed salt, the said process comprising the steps of:
  • the kainite type mixed salt used contains KCl-15-22%; NaCl-15-22%; MgSO 4 -28-40%; MgCl 2 -5-10%.
  • step (i) kainite type mixed salt is treated with water and KEL obtained in step (xvi) to leach out NaCl from the mixed salt and slurry thus obtained is filtered to yield schoenite and filtrate (SEL).
  • step (i) one part by weight of mixed salt is treated with 0.3-0.7 parts by volume of water in first batch of reaction.
  • step (i) one part by weight of mixed salt is treated with 0.75-1.25 parts by volume of KEL obtained in step (xvi) in the subsequent batches of reactions.
  • the composition of KEL obtained in step (xvi) is typically 11-14% KCl, 1-3% NaCl, 9-11% MgSO 4 , and 1-2% MgCl 2 .
  • the composition of SEL obtained in step (ii) is typically 6-12 % KCl, 5-15% NaCl, 10-20% MgSO 4 and 4-10% MgCl 2 .
  • composition of the schoenite obtained in step (ii) is 40-45% K 2 SO 4 , 30-35% MgSO 4 and 0.5-2.0% NaCl.
  • all processing was carried out under ambient conditions, preferably at a temperature in the range of 15-40°C.
  • the Ca(DPA) 2 used is prepared by treating DPA with 1-5% stoichiometric excess of lime slurry.
  • the mole ratio of DPA to lime for the preparation of Ca(DPA) 2 used is 1:0.5 to 1: 0.6.
  • step (iii) 1 mole of Ca(DPA) 2 used is treated with SEL containing 2.0-2.5 mol of KCl, preferably 0.21-0.23 mol of KCl.
  • the molar yield of K(DPA) obtained is 95-99% with respect to Ca(DPA) 2 .
  • the strength of HCl used for decomposition of K(DPA) is 5-6N.
  • the KCl solution obtained has a concentration of 12-25 %, preferably 18-22%.
  • the treatment of the aqueous KCl with schoenite improved the purity of KCl to 92-96%.
  • the molar yield of KCl obtained is in the range of 83-90% with respect to K(DPA).
  • the strength of aqueous HNO 3 used for the decomposition of residual K(DPA) is 4-6N.
  • the loss of DPA obtained per cycle is less than 1%.
  • one part by weight of schoenite used is treated with 0.3-0.5 parts by weight of KCl in the form of a concentrated solution.
  • the SOP obtained has K 2 O content in the range of 45-50%.
  • the molar yield of SOP obtained is in the range of 55-65% with respect to total K 2 O in schoenite and KCl and the balance is recycled for the decomposition of kainite mixed salt.
  • the molar yield of SOP obtained is in the range of 89-92% with respect to the K 2 O content in kainite mixed salt.
  • This example summarizes the novel SOP production process from kainite type mixed salt was produced from sea bittern and the end bittern was kept aside.
  • the mixed salt was treated with appropriate quantity of water, and KEL obtained in the process below, and the slurry was filtered to yield schoenite and a filtrate (SEL) rich in KCl but which also contained other constituents, namely NaCl, MgSO 4 , and MgCl 2 .
  • the schoenite was treated with solution of MOP in water under agitation.
  • the slurry was filtered to obtain SOP and a filtrate (KEL) rich in KCl which is recycled for schoenite production.
  • End bittern obtained during mixed salt production was desulphated and treated with lime and the slurry filtered to obtain Mg(OH) 2 and CaCl 2 -containing filtrate which was used to desulphate SEL.
  • Desulphated SEL was mixed with desulphated end bittern and evaporated to obtain carnallite.
  • the carnallite was decomposed to obtain carnallite decomposed product which was then subjected to hot leaching to obtain KCl solid.
  • the schoenite was then treated with the KCl and water to obtain SOP as described above.
  • the example further teaches us that water needs to be added into the mixture of schoenite and KCl to produce SOP and that there is an opportunity to devise a process wherein the KCl is obtained in solution form with accompanying benefits of easier processing and elimination of additional requirement of water.
  • KCl is recovered from SEL by the alternative route of the present Example that overcomes the drawbacks referred to in Example 1.
  • 100 g of DPA (0.228 mol) was reacted under ambient conditions with lime slurry containing 6.4 g (0.114 mol) of lime and 400 mL of water.
  • the reddish brown solution of Ca(DPA) 2 thus obtained was added under stirring into 200 mL of SEL containing 13.2 % NaCl, (0.226 mol%), 8.85% KCl (0.119 mol%), 5.6% of MgCl 2 (0.059 mol%) and 14.5% of MgSO 4 (0.121 mol%) over a period of 5 minute. Stirring was continued for 10 minutes.
  • the precipitate of K(DPA) and CaSO 4 formed was filtered and washed with water (3x20 mL). It was treated with 80 mL of 5 N HCl under mechanical stirring for 2 hrs and the resultant solution of KCl . was filtered and washed with water (3x25 mL). The residue containing DPA and CaSO 4 , was again treated with lime to regenerate Ca(DPA) 2 while stoichiometric amount of concentrated HCl was added into the washings for demetallation of K(DPA) in the second cycle. After five cycles, 600 mL of KCl solution was obtained whose pH was adjusted to 7.0.
  • Example 1 teaches us that although recovery of KCl with respect to K 2 O in SEL was 83.6%, the main drawbacks are: (i) 15% loss of DPA after 5 cycles, (ii) KCl solution recovered by DPA extraction method is too dilute which causes low yield (33%) of SOP, and (iii) there is as much as 8% gypsum impurity in the SOP.
  • Example 2 The experiment of Example 2 was carried out again with 88 g of DPA and 170 mL of SEL having the following composition: NaCl: 12.5% (0.214 mol%), KCl: 8.7% (0.116 mol%), MgCl 2 : 4.5% (0.047 mol%) and MgSO 4 : 18.7% (0.155 mol)%.
  • the KCl solution obtained had a concentration of 16%, which was made possible by taking twofold excess volume of 5N HCl which facilitated washing with reduced amount of water and thereby to minimize the overall volume.
  • 250 ml of solution containing 40 g of KCl (0.537 mol) was obtained, with 86.3% recovery with respect to K 2 O in SEL.
  • the present example teaches us a means of increasing the KCl concentration in solution to enhance SOP yield.
  • Example 3 The experiment of Example 3 was repeated and KCl solution having 18.4% concentration was obtained from SEL. The former was treated with a small quantity of schoenite to remove Ca 2+ impurity in the solution in the form of CaSO 4 . SOP prepared as described above using this KCl solution had purity of 92.5% with considerably reduced gypsum contamination (2.3%).
  • Examples 2 and 4 teach us that calcium contamination of KCl solution obtained from SEL can lower purity of SOP and that such Ca 2+ ions can be removed by treating the solution with a small quantitative of schoenite, filtering the solution and then finally treating with the required quantity of schoenite to produce SOP.
  • Example 4 The experiment of Example 4 was repeated with one modification, namely, the decomposition of K(DPA) with excess HCl was followed by further treatment of the residue with excess HNO 3 solution.
  • the acid solutions containing potassium salt from the decomposition of K(DPA) were recycled in subsequent batches.
  • the loss of DP after five cycles was found to be 5%.
  • This Example teaches us that HNO 3 can effect more complete decomposition of K(DPA) and DPA loss is cut down from 15% to 5% after five cycles, and the latter loss mainly is due to handling losses.
  • the KNO 3 solution can be made close to the saturation limit of this salt which can be then used for efficient recovery of solid KNO 3 or the solution can be used directly for appropriate applications.
  • This Example shows us the optimum working of the invention.
  • 60 ml of SEL (containing 10.1% KCl) was treated with stoichiometric (w.r.t. K 2 O) quantity of Ca(DPA) 2 prepared from 35 g of DPA and the resultant precipitate of K(DPA) was treated successively with aqueous HCl and HNO 3 solutions.
  • the KCl solution obtained was treated with 0.6g of schoenite and filtered to remove CaSO 4 .
  • the filtered solution containing 17.8% KCl was added to 13.1 g of schoenite and stirred for 4.5 h.
  • the precipitated SOP was isolated by filtration and dried to yield 7.4 g (59.2% w.r.t.

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Claims (15)

  1. Ein integriertes Verfahren zur Herstellung von Kaliumsulfat (SOP) aus sulfatreicher Salzmutterlauge aus kainitartigem Mischsalz, wobei das Verfahren die folgenden Schritte beinhaltet:
    (i) Behandeln des Mischsalzes mit einer angemessenen Menge Wasser in dem ersten Ansatz, um unter Umgebungsbedingungen NaCl auszulaugen und gleichzeitig Kainit in Schönit umzuwandeln,
    (ii) Filtrieren des resultierenden Schönits und separates Sammeln des als SEL bezeichneten Filtrats,
    (iii) Behandeln des obigen SEL mit einer in Bezug auf [K+] in dem SEL stöchiometrischen Menge Ca(DPA)2 (DPA = Dipikrylamin), um K(DPA) zu erhalten, das durch Behandeln von DPA mit in Bezug auf DPA 1-5 % stöchiometrischem Überschuss von Kalkschlamm erhalten wird,
    (iv) Filtrieren des obigen resultierenden K(DPA) und CaSO4 und Abscheiden des Filtrats
    (v) Behandeln des resultierenden Rests mit 2-3-fachem Überschuss von wässriger HCl-Lösung mit 5-6 N Konzentration, um den Großteil des K(DPA) abzubauen,
    (vi) Filtrieren der resultierenden Lösung aus KCl und überschüssiger Säure von CaSO4 und nicht in Reaktion getretenem K(DPA),
    (vii) Spülen des resultierenden Rests mit einer geringen Menge Wasser und Mischen der Spülung mit dem anfänglichen Filtrat von KCl,
    (viii) Behandeln des in Schritt (vii) erhaltenen verbleibenden Rests mit 10-bis-20-fachem Überschuss von 4-6 N HNO3, um Spuren von K(DPA) abzubauen und die Masse zu filtrieren und das KNO3 und HNO3 enthaltende Filtrat zurückzubehalten,
    (ix) Behandeln des obigen resultierenden Rests, der DPA und CaSO4 enthält mit in Bezug auf DPA 1-5 % stöchiometrischem Überschuss von Kalkschlamm enthält, und Filtrieren der Lösung, um einen Gipsrest und ein Filtrat, der/das zum Wiederverwerten in Schritt (iii) Ca(DPA)2 enthält, zu erhalten.
    (x) Wiederholen von Schritt (iii) mit dem in Schritt (ix) erzeugten Ca(DPA)2 und Wiederholen des Filtriervorgangs aus Schritt (iv),
    (xi) Wiederverwenden der KCl und HCl enthaltenen wässrigen Lösung, die in Schritt (vi) und (vii) erzeugt wird, zum Abbau des aus Schritt (x) erhaltenen Rests gemäß dem Verfahren aus Schritt (v), um restliche Säure aufzubrauchen und gleichzeitig die KCL-Konzentration zu erhöhen,
    (xii) Wiederverwenden der KNO3 und HNO3 enthaltenden wässrigen Lösung, die in Schritt (viii) erzeugt wird, zur vollständigen Abbaureaktion des verbleibenden Rests aus Schritt (xi) gemäß dem Verfahren aus Schritt (viii) erzeugt wird, um restliche Säure aufzubrauchen und gleichzeitig die KNO3-Konzentration zu erhöhen,
    (xiii) Aufbauen von KCl und KNO3-Konzentrationen in den Lösungen zur Sättigungsgrenze, indem die Salzlösungen und Säurelösungen mehreren Zyklen unterzogen werden, wie in Schritt (xi) bzw. (xii) beschrieben wird,
    (xiv) Behandeln der fast gesättigten KCl-Lösung, die in Schritt (xiii) erhalten wird, mit einer geringen Menge (1-5 Masseprozent von KCl) Schönit, um durch Gebrauch des Sulfats in dem Schönit Spuren von Ca2+-Unreinheiten in der Lösung in der Form von Gips auszufällen,
    (xv) Behandeln der obigen KCl-Lösung aus Schritt (xiv) mit einer stöchiometrischen Menge des in Schritt (ii) erzeugten Schönits, um SOP zu erhalten,
    (xvi) Filtrieren der obigen Lösung aus Schritt (xv), um das gewünschte SOP mit >92 % Reinheit und die Mutterlauge (KEL) zu erhalten, und
    (xvii) Wiederverwerten der in Schritt (xvi) erhaltenen Mutterlauge (KEL) in Schritt (i) für weitere Reaktionsansätze.
  2. Verfahren gemäß Anspruch 1, wobei das verwendete kainitartige Mischsalz Folgendes enthält: 15-22 % KCl; 15-22 % NaCl; 28-40 % MgSO4; 5-10 % MgCl2.
  3. Verfahren gemäß Anspruch 1, wobei kainitartiges Mischsalz in Schritt (i) mit Wasser und in Schritt (xvi) erhaltenem KEL behandelt wird, um NaCl aus dem Mischsalz auszulaugen, und auf diese Art und Weise erhaltener Schlamm filtriert wird, um Schönit und ein Filtrat (SEL) zu ergeben.
  4. Verfahren gemäß Anspruch 1, wobei in Schritt (i)
    - ein Gewichtsteil Mischsalz in einem ersten Reaktionsansatz mit 0,3-0,7 Volumenanteilen Wasser behandelt wird oder
    - ein Gewichtsteil Mischsalz in den folgenden Reaktionsansätzen mit 0,75-1,25 Volumenanteilen von in Schritt (xvi) erhaltenem KEL behandelt wird.
  5. Verfahren gemäß Anspruch 1, wobei die Zusammensetzung von in Schritt (xvi) erhaltenem KEL typischerweise 11-14 % KCl, 1-3 % NaCl, 9-11 % MgSO4 und 1-2 % MgCl2 ist oder wobei die Zusammensetzung von in Schritt (ii) erhaltenem SEL typischerweise 6-12 % KCl, 5-15 % NaCl, 10-20 % MgSO4 und 4-10 % MgCl2 ist oder wobei die Zusammensetzung des in Schritt (ii) erhaltenen Schönits 40-45 % K2SO4, 30-35 % MgSO4 und 0,5-2,0 % NaCl ist.
  6. Verfahren gemäß Anspruch 1-5, wobei jegliche Verarbeitung unter Umgebungsbedingungen ausgeführt wurde, vorzugsweise bei einer Temperatur in dem Bereich von 15-40 °C.
  7. Verfahren gemäß Anspruch 1, wobei das verwendete Ca(DPA)2 durch Behandeln von DPA mit 1-5 % stöchiometrischem Überschuss von Kalkschlamm zubereitet wird.
  8. Verfahren gemäß Anspruch 7, wobei das für die Zubereitung von Ca(DPA)2 verwendete Molverhältnis von DPA zu Kalk 1:0,5 bis 1:0,6 beträgt.
  9. Verfahren gemäß Anspruch 1, wobei in Schritt (ii) 1 Mol verwendetes Ca(DPA)2 mit 2,0-2,5 Mol KCl, vorzugsweise 0,21-0,23 Mol KCl, enthaltendem SEL behandelt wird.
  10. Verfahren gemäß Anspruch 1-9, wobei die molare Ausbeute von erhaltenem K(DPA) in Bezug auf Ca(DPA) 95-99 % beträgt und/oder wobei die erhaltene KCl-Lösung eine Konzentration von 2-25 %, vorzugsweise 18-22 %, aufweist.
  11. Verfahren gemäß Anspruch 1-10, wobei die Behandlung des wässrigen KCl mit Schönit die Reinheit von KCl auf 92-96 % verbessert hat.
  12. Verfahren gemäß Anspruch 1-11, wobei die molare Ausbeute von erhaltenem KCl in Bezug auf K(DPA) in dem Bereich von 83-90 % liegt.
  13. Verfahren gemäß Anspruch 1-12, wobei der Verlust von pro Zyklus erhaltenem DPA weniger als 1 % beträgt.
  14. Verfahren gemäß Anspruch 1-13, wobei ein Gewichtsteil verwendeten Schönits mit 0,3-0,5 Gewichtsteilen KCl in der Form einer konzentrierten Lösung behandelt wird.
  15. Verfahren gemäß Anspruch 1-14, wobei das erhaltene SOP einen K2O-Gehalt in dem Bereich von 45-50 % aufweist und/oder wobei die molare Ausbeute von erhaltenem SOP in dem Bereich von 55-65 % in Bezug auf das gesamte K2O in Schönit und KCl liegt und der Restteil für den Abbau von Kainit-Mischsalz wiederverwertet wird und/oder wobei die molare Ausbeute von erhaltenem SOP in dem Bereich von 89-92 % in Bezug auf den K2O-Gehalt in Kainit-Mischsalz liegt.
EP05850953A 2005-11-10 2005-12-27 Verbessertes verfahren zur gewinnung von kaliumsulfat (sop, sulphate of potash) aus sulfatreicher muttersole Expired - Lifetime EP1945567B1 (de)

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PCT/IN2005/000441 WO2007054953A1 (en) 2005-11-10 2005-12-27 Improved process for the recovery of sulphate of potash (sop) from sulphate rich bittern

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WO2016134435A1 (ru) * 2015-02-25 2016-09-01 Государственное научное учреждение "Институт Общей и Неорганической Химии Национальной академии наук Беларуси" Способ переработки полиминеральных калийных руд с получением сульфата калия

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EP2411330B1 (de) * 2009-03-27 2013-08-14 Council of Scientific & Industrial Research Verfahren zur gleichzeitigen herstellung von kaliumsulfat, ammoniumsulfat, magnesiumhydroxid und/oder magnesiumoxid aus kainit-mischsalz und ammoniak
CN102503619B (zh) * 2011-09-02 2013-11-06 天津科技大学 由制盐母液制取复合肥的方法
UA113204C2 (xx) * 2012-04-02 2016-12-26 Селективна екстракція хлориду калію з відхідного шенітового розчину з використанням тартратної кислоти як безпечного м'якого екстрагента, придатного до рециркуляції
WO2014033687A1 (en) * 2012-09-02 2014-03-06 Council Research Scientific Industrial Research Integrated process of production of potassium sulphate and ammonium sulfate from kainite mixed salt
CN105849046B (zh) * 2013-07-31 2018-05-04 浦项产业科学研究院 用于制造钾化合物的装置和从盐水中回收钾化合物的方法
WO2016059651A1 (en) * 2014-10-16 2016-04-21 Council Of Scientific And Industrial Research A process of production of potassium ammonium sulfate compound fertilizer in cost-effective manner directly from concentrated sea bittern
RU2649872C1 (ru) * 2017-07-24 2018-04-05 Федеральное государственное бюджетное образовательное учреждение высшего образования "Вятская государственная сельскохозяйственная академия" (ФГБОУ ВО Вятская ГСХА) Способ электролитической обработки отходов растительного сырья
CN115304083B (zh) * 2022-08-25 2023-07-07 湖北振华化学股份有限公司 一种芒硝制取硫酸钾生产过程中钾芒硝母液循环提溴的方法
WO2024059126A1 (en) * 2022-09-14 2024-03-21 U.S. Borax, Inc. Beneficiating sodium sulfate-containing material
CN118851511B (zh) * 2024-09-26 2025-03-04 中国海洋大学 一种盐碱地农田灌溉废水的资源化利用方法和应用

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EA030375B1 (ru) * 2015-02-25 2018-07-31 Государственное научное учреждение "Институт Общей и Неорганической Химии Национальной академии наук Беларуси" Способ переработки полиминеральных калийных руд с получением сульфата калия
DE112015006221B4 (de) 2015-02-25 2022-06-02 Limited Liability Company "K-Potash Service" Verfahren zur Verarbeitung von polymineralischen Kaliumerzen unter Gewinnung von Kaliumsulfat

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CA2538493A1 (en) 2007-05-10
AU2006200932B2 (en) 2012-05-24
IL190373A0 (en) 2009-09-22
CN1962443A (zh) 2007-05-16
AU2006200932A1 (en) 2007-05-24
WO2007054953A1 (en) 2007-05-18
US8182784B2 (en) 2012-05-22
US20100266482A1 (en) 2010-10-21
EP1945567A1 (de) 2008-07-23
JO2595B1 (en) 2011-02-27
ES2347673T3 (es) 2010-11-03
DE602005022506D1 (de) 2010-09-02
ATE474815T1 (de) 2010-08-15
CA2538493C (en) 2009-05-26
CN1962443B (zh) 2010-05-12

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